Quaternary thenyl ammonium salts

ABSTRACT

QUATERNARY THENYL AMMONIUM SALTS, I.E. ((OPTIONALLY 2, 3, 4 AND/OR 5 HALO, ALKYL, CYANO, ALKOXYCARBONYL, AND/OR NITRO-SUBSTITUTED)-5 OR 4-THENYL)-(TRI(SAME OR MIXED) ALKYL, ALKENYL, ALKINYL, SUBSTITUTED ALKYL, CYCLOALKYL, HETEROCYCLIC AND/OR ARYL)-AMMONIUM SALTS, I.E. HALIDES, NITRATES, AZIDES, THIOCYANATES, SULFATES, PHOSPHATES, O-ETHYLXANTHATES, ETC., WHICH POSSESS PLANT-GROWTH REGULATING PROPERTIES, INCLUDING SYNERGISTIC PROPERTIES.

United States Patent "ice 3,748,343 QUATERNARY THENYL AMMONEUM SALTS Peter F. Epstein, Prairie Village, Kans., Joseph R. Cafirey, Independence, Mo., and Pyung Kyung Yu, Overland Park, Kane, assignors to Chemagro Corporation, Kansas City, M0. N0 Drawing. Filed Feb. 17, 1971, Ser. No. 116,258 Int. Cl. Ctl7d 63/14 U.S. Cl. 260-3325 8 Claims ABSTRACT OF THE DISCLOSURE Quaternary thenyl ammonium salts, i.e. [(optionally 2, 3, 4 and/ or 5 halo, alkyl, cyano, alkoxycarbonyl and/ or nitro-substituted)-5 or 4-thenyl]-[tri(same or mixed) alkyl, alkenyl, alkinyl, substituted alkyl, cycloalkyl, heterocyclic and/ or arylJ-ammonium salts, i.e. halides, nitrates, azides, thiocyanates, sulfates, phosphates, O-ethylxanthates, etc., which possess plant-growth regulating properties, including synergistic properties.

The present invention relates to and has for its objects the provision of particular new quaternary thenyl ammonium salts, i.e. [optionally 2,3,4 and/or 5-mono-di and tri [same or mixed] halo, alkyl, cyano, alkoxycarbonyl, and/ or nitro substituted)-5- or 4-thenyl]-[tri(same or mixed) alkyl, alkenyl, alkinyl, substituted alkyl, cycloalkyl, heterocyclic and/ or aryl]-ammonium salts, i.e. halides, nitrates, azides, thiocyanates, sulfates, phosphates, O-ethyl xanthates, N-methyl-dithiocarbamates, etc., which possess valuable plant-growth regulating properties, including synergistic properties; active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles; and methods for producing such compounds and for using such compounds in a new way, especially for regulating, e.g., selectively retarding and/ or promoting, the growth of plants or vegetation of the most varied kinds, including synergistic plant growth regulation, with other and further objects of the invention becoming apparent from a study of the within specification and accompanying examples.

It is known in the prior art that compounds such as the quaternary ammonium compound (2-chloroethyl)-trimethyl ammonium chloride (Cycosel) of the formula 69 6 ClCH CH N(CHa)a.Cl

4 1 I s/ e R CH NqRlX 3,748,343 Patented July 24, 1973 R O2NR5.X A i (I in which exhibit strong growth-controlling, in particular growthinhibiting, eifects without significant concomitant phytotoxic effects.

It has furthermore been found, in accordance with the present invention, that the compounds of Formulae Ii and Iii above may be produced by a process which comprises reacting a corresponding thenyl halide of the formula R jomv R OHY l J:

in which IRA-L R R and R are the same as defined above, and Y is halogen with a tertiary amine of the formula R4 NCRI R (III) in which R R and R are the same as defined above,

optionally in the presence of a solvent.

The nature of the anionic portion of the resulting molecule of the specific halide compound of Formula Ii or Iii above so produced, i.e. X as defined above, can be varied, for example, by further reacting such specific halide compound of Formula Ii or Iii with the alkali metal (e.g. sodium, potassium, and the like) or silver salt (IV) of the desired anion, by the use of a suitable anion exchange resin, or in other conventional ways which are readily apparent to anyone skilled in the art.

Surprisingly, the compounds of Formulae Ii and Iii above according to the present invention show a more pronounced growth regulatory activity, than the analogous quaternary ammonium compounds known from the prior art, such as compound (A) noted above, which is chemically the closest active compounds having the same type of activity.

Furthermore, according to the teachings of N. E. Tolbert (loc.cit.) the compounds corresponding to his invention are derivatives of trimethyl amine, whereas the compounds of the present invention show their greatest activity when at least one or preferably more than one of the groups R R and R is C alkyl; or in which the sum of the carbon atoms in R R and R taken together lies between about 9 and 15.

The course of the anion exchange reaction in which 2- bromo-S-thenyl-(tri-n-butyl)-ammonium chloride (1) and silver nitrate are used as starting materials can be represented by the following equation:

(1) (IVE) Advantageously, in accordance with the present invention, in the various formulae herein:

R R and R each individually represents hydrogen; halo such as chloro, bromo, iodo and/or fiuoro, especially chloro and/or bromo; straight and branched chain lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.-butyl, and the like; cyano; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl isobutoxycarbonyl and the like; or nitro. R, R and R each individually represents straight and branched chain alkyl hydrocarbon of 1-12 carbon atoms such as methyl to tert.-butyl inclusive as defined above, pentyl, isopentyl, hexyl, heptyl, nand isooctyl, nonyl, decyl, undecyl, dodecyhand the like, especially lower alkyl, C or C alkyl, and C or C C and C alkyl, and more especially n-butyl (i.e. n-Bu), iso-butyl, npropyl, n-pentyl and isopentyl. alkenyl hydrocarbon such as vinyl, allyl and the like alkinyl hydrocarbon such as propargyl and the like substituted alkyl, such as cyanoalkyl, alkoxyalkyl and the like cycloalkyl such as cyclohexyl, cyclopentyl and the like heterocyclic such as morpholino and the like aromatic hydrocarbon such as phenyl, substituted phenyl and the like such that R R and R are the same or different or that R and R taken together represent a saturated heterocyclic moiety. X is an anion derived from an inorganic acid such as e.g., nitric, nitrous, sulfuric,

phosphoric, boric, hydrothiocyanic, cyanic, perchloric, periodic, hydrocyanic, carbonic, hydrofluoric, hydrochloric, hydrobromic, hydroiodic, hydrazoic acid or hydrogen sulfide or from an organic acid such as alkanoic acids, i,e., (same or mixed) mono, di, or tri-bromo, chloro or fluoro-acetic, n-, or iso-propionic, niso-, or tert-butyric, etc., acids or substituted carboxylic acid such as (same or mixed) mono, dior tribromo, ohloro or fluoro alkoxy or aryloxy (e.g., 2,4-dichloro phenyl or 2,4-dichlorophenoxy) acetic acid, or aryl alkanoic acid such as phenylacetic acid or from an aromatic acid such as benzoic (same or mixed) mono-, di-, or tri-iodo, bromoor chlorobenzoic acid, or methoxybenzoic, nitrobenzoic;

or from a carbonic acid such as e.g., methyl, ethyl, nand isopropyl, n-, iso, secand tert-butyl, etc., thiocarbonic acid, phenyl thiocarbonic and (same or mixed) mono-dior tri-chloro, bromo, iodo, lower alkyl, alkoxy, phenyl carbonic acid and the corresponding dior tri-thiocarbonic acids;

or mono or di- (same or mixed) alkyl or aryl monodi-, trior tetra-thiophosphosphoric; mono, dior trithiophosphonic or mono-dithio-phosphinic acids, e.g., 0,0-diphenyl phosphonothioic acid, O-alkyl methanephosphonothioic acid diphenyl phosphinodithoic acid, etc.

or alkyl and aryl sulfonic and sulfinic acid, e.g. benzene sulfonic acid, methanesulfinic acid, etc.

or in which X is an anion derived from a mercaptan R' SH (i.e., has the structure 8R) in which R is alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, heterocyclic and the like.

It will be noted that the point of attachment of the nitrogen bearing side chain to the thiophene ring can be either in the 4- or 5- position of the nucleus depending on the intermediate used and on the nature of the substituents R R and R Most preferably, R R and R are hydrogen, bromo, chloro, cyano or alkoxycarbonyl; R R and R are each lower alkyl; and X is a monovalent anion such as chloride, nitrate, thiocyanate or azide.

Preferred compounds of the present invention include (1) (Z-bromo-5-ethenyl)-(tri-n-butyl)-ammonium chloride (2) (2-bromo-S-thenyl)-(tri-n-butyl) -ammonium nitrate (3) (2-bromo-5-thenyl)- (tri-n-butyl) -ammonium thiocyanate (4) (2-chloro-5-thenyl)-(tri-n-butyl) -ammonium chloride (5 (2,5-dichloro-4-thenyl) (tri-n-propyl) -ammonium chloride (6) (2-chloro-5-thenyl) (tris-iso-amyl -ammonium chloride (7) (2-bromo-5-thenyl) -(tris-iso-amyl) -ammonium chloride (8) (Z-bromo-S-thenyl)-(methyl-di-iso-butyl)-ammonium chloride (9) (2,5-dibromo-4-thenyl)-(tri-n-propyl)-ammonium chloride (10) (Z-bromo-S-thenyl)-triethyl-ammonium chloride l 1 (2,5 -dibromo-4-thenyl (tri-n-butyl) -ammonium chloride l2) (2-bromo-5-thenyl) -(tri-i-n-propyl) -ammonium chloride 1 3 (Z-bromo-S-thenyl) (methyl-di-n-butyl -ammonium chloride 14) Z-bromo-S-thenyl) allyl-dlielthyl ammonium chloride 1 15) 2-bromo-5-thenyl) (ethyl-di-iso-propyl) -ammonium chloride l6) (Z-chloro-S-thenyl) (cyclohexyl-dimethyl) ammonium chloride 17) (Z-bromo-S-thenyl )-(cyc1oheXyl-dimethyl) ammonium chloride (l8) (2-chloro-5-thenyl)-(methyl-diethyl -ammonium chloride 19) (2-bromo-5-thenyl) (methyl-diethyl ammonium chloride (20) (Z-bromo-S-thenyl)-(phenyl-dimethyl)-ammonium chloride (21) (2-chloro-5-thenyl (phenyl-dimethyl) -ammonium chloride (22) 2-thenyl-triethyl-ammonium chloride (23) (2,5-dichloro-4-thenyl)-triethyl-ammonium chloride (24) 2-thenyl- (tri-n-butyl)-ammonium chloride (25) (Z-bromo-S-thenyl)-trimethyl-ammonium chloride (26) (2,S-dichloro-4thenyl)-(tri-n-butyl) ammonium chloride (27 (2-chloro-5-thenyl) (tri-n-propyl) -ammonium chloride (28) (2-chloro-5-thenyl)-(methyl-di-n-butyD-ammonium chloride (29) (2,5 -dichloro-4-thenyl) (methyl-di-n-butyl) ammonium chloride (30) (2-chloro-5-thenyl)- (tris-n-amyl) -ammonium chloride (31 Z-bromo-S-thenyl) (tris-n-amyl) -ammonium chloride 32) (Z-bromo-S-thenyD-trimethyl-ammonium nitrate (3 3 (2,5 -dichloro-4-thenyl tri-n-butyl) -ammonium chloride (34) 2,5 -dichloro-4-thenyl) (tri-n-butyl) -ammonium chloride (35 (2-chloro-5-thenyl) (allyl-dimethyl) ammonium chloride (3 6) (2-bromo-5-thenyl) (2-cyanoethyl) -diethyl] ammonium chloride (37) (2-chloro-5-thenyl)- (Z-cyanoethyD-diethyl] ammonium chloride (3 8) (2-chloro-5-thenyl- (methyl-di-iso-butyl) ammonium chloride (39) (2,5-dichloro-4-thenyl) -(methyl-di-iso-butyl) ammonium chloride (40) (2,5-dichloro-4-thenyl)-N-ethyl-morpholinium chloride (41) (2-chloro-S-thenyl)- (tris-propargyl)-ammonium chloride (42) (2-bromo-5-thenyl) (tris-propargyl) -ammonium chloride (43 (2-chlo ro -5-thenyl -N-ethyl-morpholinium chloride (44) 2-b romo-S -theny1 -N-ethyl-morpholinium chloride (45 2-chloro-5-thenyl -N-phenyl-morpholinium chloride (46) (2-bromo-5-thenyl -N-phenyl-morpholinium chloride (47) (2-chloro-5-thenyl)-triallyl-ammonium chloride (48) (2-bromo-5-thenyl -triallyl-ammonium chloride (49) (2,5-dichloro-4-thenyl)-triallyl-ammonium chloride (50) (Z-cyano-S-thenyl)-(tri-n-butyl)-ammonium chloride 5 1 2-bromo-3-methyl-4-thenyl -tributyl-ammonium chloride (5 2) (2-chloro-5-thenyl) -(cycloheXyl-dimethyl)- ammonium, N,N-dimethyl dithio carbamate 5 3) (2-iso-butoxycarbonyl-5-thenyl) -(tri-n-butyl)- ammonium chloride (54) (2-iso-butoxycarbonyl-S-thenyl)- (tris-iso-amyl)- ammonium chloride (55 (2-iso-butoxycarbonyl-S-thenyl)-(methyl-dis-isobutyl)-ammonium chloride 5 6) (2-bromo-5-thenyl)-(tri-n-butyl)-ammonium azide 5 7 (2-chloro-5-thenyl (tri-n-butyl) -ammonium nitrate v (5 8) (2-chloro-5-thenyl (tri-n-butyl -ammonium thiocyanate In accordance with one embodiment of the present invention, R R and R each individually is hydrogen; or

one or more is selected from the group consisting of chloro, bromo, lower alkyl of C carbon atoms, lower alkoxycarbonyl of 1-5 carbon atoms, cyano or nitro;

R R and R each individually are lower alkyl groups of 1-5 carbon atoms, alkenyl groups of 2-5 carbon atoms or cycloalkyl groups of 4-7 carbon atoms;

and X is a chloride, nitrate or thiocyanate ion;

and more specifically, in Formula Ii above, R is chloro or bromo, R and R are both hydrogen, R R and R are selected from n-butyl, iso-butyl, iso-amyl, methyl, ethyl, n-propyl, cyclohexyl and iso-propyl; with the proviso that the total number of carbon atoms in R R and R taken together lies between about 8 and 16; and X4 is a chloride, nitrate or thiocyanate ion; whereas in Formula Iii above, R and R are both chloro or bromo, R is hydrogen, and R R R and X have the same meanings as defined above.

Preferably, R R and R each individually is hydrogen or halo, especially chloro or bromo; R R and R each individually is C alkyl, especially C or C or C C or C alkyl; or cyclohexyl, or phenyl; and X is a halide, especially chloride ion or a nitrate ion; or a thiocyanate ion, or an azide ion.

More particularly R and R each individually is hydrogen; or chloro; or bromo; R is hydrogen; R R and R are individually n-propyl, iso-propyl, n-butyl, iso-butyl or iso-amyl and X is a chloride ion or a nitrate ion or a thiocyanate ion.

Most particularly, in Formula Ii above, R is bromo or chloro R and R are both hydrogen; R R and R individually are n-butyl, n-propyl, iso-amyl, or iso-butyl, or methyl, provided that the total number of carbon atoms in R and R and R taken together lies between about 9 and 15, and X is a chloride, nitrate or thiocyanate ion; whereas in Formula Iii above, R and R are both chloro, or both bromo, R is hydrogen, and R R R and X have the meanings as defined above.

The types or" starting thenyl halides usable in accordance with the process of the present invention are clearly characterized by Formulae Hi and IIii noted above.

These starting compounds are well known and can be prepared readily on an industrial scale. (See e.g. Henry D. Norris, US. Pat. 2,623,049).

As examples of such starting thenyl halides which can be used in accordance with the present invention, there may be mentioned in particular:

Z-thenyl chloride 3-thenyl bromide 2-chloro-5-thenyl chloride 2-bromo-5-thenyl chloride 2-rnethyl-5-theny1 chloride 2,5-dichloro-4-thenyl chloride 2,5-dibromo-4-thenyl chloride 2,3,5-trichloro-4-thenyl chloride 2,3,4-trichloro-5-thenyl chloride 2,3,4-tribromo-5-thenyl chloride 2-nitro-5-thenyl chloride 2-chloro-4-nitro-5-thenyl chloride 2,5-dichloro-3-nitro-4-theny1 chloride 2-ethoxycarbonyl-5-thenyl chloride 2-isobutoxycarbonyl-S-thenyl chloride 2-cyano-5-thenyl chloride 2-bromo-5-chloro-3-thenyl chloride 5-iodo-2-thenyl chloride 5-fluoro-2-thenyl chloride 2-methyl-5-chloro-3-thenyl chloride 2,5-dimethyl-3-thenyl chloride, and the like.

The types of starting trialkyl or other tertiary amines usable in accordance with the process of the present invention are clearly characterized by Formula III noted above.

These starting compounds are also well known and can be prepared readily on an industrial scale.

As examples of such starting trialkylamines or other tertiary amines which can be used in accordance With the present invention, there may be mentioned in particular:

tri-n-butyl amine tri-iso-butyl amine tris-iso-amyl amine methyl-di-iso-butyl amine tri-n-propyl amine and the like.

The production reaction is carried out preferably in the presence of a solvent (this term includes a mere diluent), particularly one in which the solubility of the final product is not very high and which is inert to the reaction. Examples of such solvents include inert organic solvents, for example, hydrocarbons such as n-hexane, nheptane, benzine, benzene and toluene; ethers such as diethyl ether, dioxane and tetrahydrofuran; lower boiling aliphatic nitriles such as acetonitrile; amides such as dimethyl formamide; alkyl sulfoxides such as dimethyl sulfoxide; aliphatic ketones such as acetone; chlorinated aliphatic hydrocarbons such as chloroform and dichloromethane; and the like; aliphatic alcohol esters of aliphatic carboxylic acids such as ethyl acetate and the like; and any desired mixtures of these solvents.

The use of anhydrous and non-hydroxylic solvents and the absence of oxygen are desirable factors in the optimization of yield and product quality but are not essential to the success of the reaction.

The reaction temperature can be varied within a fairly wide range. In general the reaction is carried out at substantially between about 20 C. and +130 C. preferably between about 20 C. and 80 C.

In general, for economy and efficiency, the reactants are used in approximately equimolar proportions. The reaction can, for example, be carried out in such a manner that the thenyl halide, for example 2-bromo-S-thenyl chloride, is added to a solution of the amine, for example tri-n-butyl amine, in anhydrous acetonitrile at room temperature, and the reaction mixture heated under reflux for several hours, followed by removal of solvent. The resulting solid crystalline product can be obtained in a substantially pure form by recrystallization from a suitable solvent.

The 5- (or 4-) thenyl trialkyl ammonium halides thus prepared can, if desired, be converted into other anionic ammonium salts of the desired anionic component in the conventional manner in a solvent such as acetone, ethanol or dimethyl formamide in which both of the reagents are appreciably soluble. After separation of the metal halide (e.g. sodium, potassium, silver, and the like halide) formed in the reaction, removal of the solvent under reduced pressure yields the desired salt in substantially pure form. Alternatively, a suitable anionic exchange resin can be employed.

Advantageously, the active compounds according to the present invention exhibit strong growth-regulatory properties. Such compounds can therefore be used to affect the rate of growth of plants. Since at rates and in concentrations showing high growth regulatory activity the instant active compounds have little or no phytotoxic action, these effects on plant growth can be obtained with little or no damage to useful plants. The instant compounds also possess comparatively low mammalian toxicity.

By plants are meant in the broadest sense all useful vegetation including valuable agricultural, horticultural, fruiticultural, and the like, crop vegetation, weeds, etc., the growth regulation of which is desired.

Thus, the active compounds according to the present invention can be usedfor stunting or retarding the growth of monocotolydenous and dicotolydenous crop and weed plants, ornamental plants, shrubs, and trees;

for increasing beneficially the yield, oil yield and protein yield of leguminous plants such as soybeans, lima beans, snap beans, peas, and the like;

for increasing the sugar content or yield of plants such as sugar beet, sugar cane, and the like;

for affecting the fruit set of spermatophytic plants, i.e., apples, peaches and other fruit of fruitbearing trees, shrubs or crop plants;

for increasing the yield of cotton plants;

for increasing the resistance of vegetation, particularly fruit trees, to the damage caused by frost and drought;

for retarding the growth of grasses such as Kentucky bluegrass, fescue, and the like, by reducing both the clipping weight per unit area and the plant height, and thus providing a means of chemical mowing;

for increasing the yield or general commercial value of various food crop plants such as coffee, tea, cocoa, dates, coconuts, bananas and the like;

for enhancing synergistically the action of maleic hydrazide (MH-30) in retarding the growth of grasses such as Kentucky bluegrass, fescue, and the like, by reducing both the clipping weight per unit area and the plant height, thus also providing such chemical moving;

for reducing synergistically the tendency of maleic hydrazide (MH30), when used alone at comparable rates, to produce phytotoxic injury to grass plants such as Kentucky bluegrass, fescue, and the like;

for increasing the yield of natural products extracted from plants on a commercial scale, e.g. alkaloids, pyrethrins, rubber and the like;

for inhibiting or partially inhibiting the undesirable growth of suckers on plants, particularly tobacco plants;

for enhancing synergistically the effect of maleic hydrazide (MH 30) for the aforesaid use of inhibiting undesirable growth of suckers on plants, without inflicting appreciable phytotoxic damage or otherwise affecting adversely the quality of the crop;

for affecting, i.e., breaking the dormancy of plants, such as potato plants and the like, by causing them to sprout.

As aforesaid, significantly, the instant active compounds can be used in the form of foliar sprays without appreciable phytotoxicity or destruction of chlorophyll, i.e. at the biologically efficacious rates normally applied.

The active compounds according the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional, preferably inert (i.e. plant compatible or herbicially inert), pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compound with conventional pesticide dispersible liquid diluent carriers and/ or dispersible solid carriers, optionally with the use of carrier vehicle assistants, e.g., conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents whereby, for example, in the case Where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for the purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. dichloromethane, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. 2-aminoethanol, etc.), ethers, ether-alcohols (e.g. Z-methoxyethanol, etc.), amides (e.g. dimethyl formamide etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g.

acetone, etc.) and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolin, alumina, silica, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as conventional plantgrowth regulators, fungicides, insecticides, nematicidcs bactericides, selective herbicides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.195%, and preferably -90%, by weight of the mixture, whereas carrier composition mixtures suitable for direct application of field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0l5.0%, preferably 0.01-0.8%, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. surface active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.01-95%, and preferably 0.0l-5.0%, by weight of the mixture.

Conveniently, the instant active compounds, having appreciable solubility in water, are preferably usable in the form of aqueous solutions containing substantially between 0.01% and 5%, preferably 0.01%0.8%, by weight of the active compound, with or without the addition of stabilizer, surface active agents, etc., as mentioned above. Such solutions are particularly useful for direct foliar spray application, in which as noted above (unlike the analogous quaternary phosphonium compounds of the prior art) they do not cause appreciable phytotoxic plant injury at efiicacious growth regulating rates of application.

The active compounds can also be used in accordance with the wall known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely dvided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by Weight of the active compound or even the 100% active substance alone, e.g. about 20- 100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively controlling the rate of growth of plants; e.g. stunting plant growth, increasing plant or fruit yield, protein yield, oil yield, sugar yield, resistance to frost and drought damage; synergizing defoliating action and inhibiting regrowth; effecting chemical mowing; preventing the growth of undesirable suckers; breaking plant dormancy and the like; which comprise applying to at least one of (a) such plants and (b) their habitat, i.e. the locus to be protected or controlled, an efficacious or growth rate controlling amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for example, by spraying, atomizing, scattering, dusting, watering, sprinkling and the like, either to the soil around the plants, themselves, or both.

It will be realized, of course, that in connection with the use of the instant compounds for influencing the growth of plants and/or effecting the other desirable results heretofore mentioned, the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application and may be varied within a fairly wide range depending upon the weather conditions, the purpose for which the active compound is used, e.g. growth promoting or growth retarding effect, and the plant species in which it is intended to produce the desired effect. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The outstanding growth regulatory activity of the particular active compounds of the present invention is illustrated, without limitation, by the following examples.

EXAMPLE 1 Cucumber Root Growth Test Wettable powder base consisting of:

92 parts by weight hydrated silica (ultra fine, Hi-Sil 4 parts by weight sodium lignin sulfonate (Marasperse 4 parts by weight polycondensate of ethylene oxide, propylene oxide and propylene glycol (bol. wt. about 1000) Pluronic L-61) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated wettable powder base, and the resulting mixture is diluted with water to the desired final concentration. A piece of round filter paper (150 mm. diameter) is placed in a 150 mm. x 25 mm. Petri dish, and 10 cucumber seeds are arranged in a row on the paper. The filter paper is then moistened with 7 mls. of the preparation of the given active compound.

The so-treated dish is incubated in darkness at 22 C. Rating is determined on the basis of growth response of the root during the period of twenty-four (24) hours between the third and fourth day of incubation.

A 0 to 9 scale rating is used to indicate the activity of potential growth retardants. A 0 scale reading indicates growth retardation with the range of 0-10% as compared with the control. A 9 scale reading corresponds to or more growth retardation. On the other hand, figures in parentheses indicate growth promotion or enhancement. Thus, a (0) to (9) scale rating is used to indicate the activity of potential growth promotants. (0) indicates growth promotion within the range of 0- 10% as compared with the control, whereas (9) indicates 90% or greater growth promotion when compared with the control.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 1.

TABLE 1 Continued TABLE 1Continued Active compounds Concentration in -p Active compounds 10,000 1,000 100 GB 9 U aN( a u):- l ml lo, S

-CH IL CH (IE-CH 1 01 s 2[ a 2- I le 6 Br CHaN-CHaCHzCN-Cl 1 it Q 6 Cl CHzN-CHzCHaCN-Cl (38) W on: 9 C1 CHaNG-BHMCI 39 CH i e CHzN(i-B11) 2- Cl 6 ell l! 8 (40).... $/CH2CH:\

/CH2N\ /O-Cl I CHaCHa l II M C1 s Cl Et CHICHI CHzN 0 01 Concentration (p.p.m.

(46).- OHaCHz 9 9 2 Br L J-JJHETQ OQJI S EXAMPLE 2 Snap Bean Foliar Spray Test To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated wettable powder base, and the resulting mixture is diluted with water, containing 0.01% polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier, to the desired final concentration.

Snap bean plants, as soon as the primary leaves are relatively smooth (6-7 days old) and are capable of absorbing and translocating chemicals, are sprayed, (treated) with the given active compound preparation at the indicated concentration until just dew moist. For each test 40 mls. of the appropriate compound dilution are sprayed on 4 plants in an area of five square feet.

The so-treated plants are moved to a greenhouse and remain there for 10 to 14 days. The degree of growth response is determined by measuring three parameters: Total plant height (A), length of second node to apex (B), and petiol length of the first trifoliate leaves (C).

A 0 to 9 scale reading is used to express the degree of potential growth retardation. A 0 scale reading indicates growth retardation within the range of 0% to 10% as compared with the control. A 9 scale reading corresponds to or more growth retardation.

A (0) to (9) scale rating is used to indicate the activity of potential growth promotants. (0) indicates growth promotion within the range of 010% as compared with the control, whereas (9) indicates 90% or greater growth promotion as compared with the control.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 2.

TABLE 2-Contim1ed Concentration (p.p.m.)

Activecompouud A B C A B C A B C CH] Cls --CHsg(i-Bu):-C1

(39).: tim 354000000 CHaNfi-BifirCl Q C1- s Cl 6 6 Br- CHihKCHs'IZECHJ -Gl 0 2 1 0 2 2 0 1 0 Q/CHSCE! e C1 S -GH,N O-Gl @CHAJQ:

0 0 o 0 1 1 0 0 0 (46) l 1 ernon, 9 Br 8 GHQI?\ 0-01 @CHiCfir G9 9 Cl- CH:N(CH CH=C s)|-Cl H CH CH-CH 1 Brs G :N( a 2):-

(1H CH CH-OH 1 1- 2N( s):-

1 Indicates compound was phytotoxle.

EXAMPLE 3 Pole bean plants, as soon as the primary leaves are relatively smooth (6-8 days old) and are capable of Pol Be Foli r S ray T t absorbing and translocating chemicals, are sprayed (treated) with the given active compound preparation 1 d b on i fin f; at the indicated concentration until ust dew moist. for wettab epo g each test 40 mls. of the appropriate compound dilution 92 parts by weight hydrated silica (ultra fine, Hi-Sil 4 parts by weight sodium lignin sulfonate (Marasperse 4 parts by weight polycondensate of ethylene oxide, propylene oxide and propylene glycol (M01. wt. about 1000) (Pluronic L-61) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated wettable powder base, and the resulting mixture is diluted with water, containing 0.01% polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier, to the desired final concentration.

are sprayed on 4 plants in an area of five square feet.

The so treated plants are moved to a greenhouse and remain there for 10 to 14 days. The degree of growth response is determined by measuring three parameters: total plant height (A), length of second node to apex (B), and petiol length of the first trifoliate leaves (C).

A 0 to 9 scale reading is used to express the degree of potential growth retardation. A 0 scale reading indicates growth retardation Within the range of 1% to 10% as compared with the control. A 9 scale reading corresponds to or more growth retardation.

A (0) to (9) scale rating is used to indicate the activity of potential growth promotants. (0) indicates growth promotion within the range of 040% as compared with the control, whereas (9) indicates 90% or greater growth promotion as compared with the control.

21 The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 3.

22 EXAMPLE 5 Chemical mowing of Kentucky bluegrass Solvent: 9.5 ml. of water containing 0.01% by weight TABLE 3.-POLE BEAN FOLIAR SPRAY TEST Petiol 2d interlength Plant medial oi tritoli- Ratings Cone. height distance ate lea! Active compound (I -pm.) (cm.) (A) (em.) (B) (0111.) (C) A B C (1) 10,000 7.0 2.7 0.8 8 9 8 1,000 9.5 4.2 2.0 7 8 7 G e 100 15.7 10.8 6.2 5 6 1 Br B CHaN(n-Bu)a-Cl A G9 9 10,000 16.8 11.6 5.4 5 6 1 OlCHgCHzNMBa-Cl 1,000 l 19.15 14.5 6.8 4

(known) Onntml 38.7 33.3 6.7 1:22:27:

EXAMPLE 4 of polyoxyethylene sorbitan monolaurate (Tween 20) Snapbean Yield Test Solvent: 9.5 ml. of water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rate of application indicated below in p.p.m.

Snap bean plants, when to of the flowers are in bloom, are sprayed (treated) with the given active compound preparation at a rate of 92.625 decaliters per hectare. The control plots receive no such treatment.

At harvest time the fresh weight of fruit from the treated and untreated plots is determined. The increase in yield of the treated plots is expressed as a percentage of the control yield.

The particular active compound tested, the rate of application and the results obtained can be seen from the following Table 4.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

The preparation of the mixture of the particular active compound with maleic hydrazide (MI-L30) is made by mixing together one part by Weight of the given active compound and three parts by weight of maleic hydrazide (MH-30), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

Growing bluegrass sod is sprayed with the particular active compound preparation at the concentrations indicated. The treatment test plots are arranged in a randomized block design with 3 replications. The plots are mowed to a uniform height of 5 centimeters before spraying and then left for 5 weeks before readings are taken.

The degree of efficacy of the particular active compound is evaluated as follows:

(i) Grass growth by visual ratings that are based on a 0 to scale, where 0 indicates no reduction in growth when compared with the control plots and 100 indicates complete suppression of additional grass growth.

(ii) In the case of the most active treatments, a clipping from a 30 cm. x 30 cm. area at a height of 2.45 cm. from the ground was taken to determine the foliage yield from each plot, and expressed as a percentage of the check.

The particular active compound tested, the rates of application and the results obtained can be seen from the following Table 5.

TABLE 5.CHEMICAL MOWING OF KENTUCKY BLUEGRASS Lbs/acre of- Average fresh green Percent Active Maleic weight of reduction compound hydrazide Visual the clipin clipping Active compound applied applied rating pings (g.) weight B -(JH 1% B 91 r \S z u):-

(1);:21'37. Same as ab0ve-.::::'::-.':;T.T::: 3. 3 0 (1) o- 0 825 2.476 (1) do. 0 4. 2 1) do- Y I Y 0 2. 5 Control 0 0 23 EXAMPLE 6 Chemiml mowing of Merion bluegrass Solvent: 9.5 ml. of water containing 0.1% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

The preparation of the mixture of the particular active compound with maleic hydrazide (MH-30) is made by mixing together one part by weight of the given active compound and either 0.5 or 2 parts by weight of maleic hydrazide (ME-30), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

Growing bluegrass sod is sprayed with the particular active compound preparation at the concentrations indicated. The treatment test plots are arranged in a randomized block design with 3 replications. The plots are mowed to a uniform height of 5 centimeters before spraying and then left for 5 weeks before readings are taken.

The degree of efficacy of the particular active compound is evaluated as follows:

The height (in cm.) of plants in 3 randomized positions in each of the 3 replicates was measured and averaged to determine the average plant height in each plot, and

24 EXAMPLE 7 Chemical pruning of elm trees Solvent: 9.5 ml. of water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

The preparation of the mixture of the particular active compound with maleic hydrazide (MH-) is made by mixing together one part by weight of the given active compound and 3 parts by weight of maleic hydrazide (MH-30), mixing 0.5 g. of the resulting mass with the stated amount of solvent containing the stated amount of emulsifier, and then further diluting the concentrate so produced with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

Three-year-old American elm trees are used as test plants. The treatments are applied by spraying the given preparation on 2 limbs per tree with 3 replications. The retardation of twig growth is determined by measuring the length of the twig 17 weeks after treatment and comparing it to the length of the same twig before treatment. The percentage growth of the twig is compared with the percentage growth of untreated twigs, and the result expressed as percent inhibition of growth of the treated twigs.

The particular active compound tested, the rates of application and the results obtained can be seen from the 5 following Table 7.

TABLE 7.CHEMIGAL PRUNING 0F ELM TREES [Means of 2 tests] Percentage Active inhibition compound Plant of growth applied height of treated Active compound (p.p.m.) (cm. twig Br S CHN(n-Bu) 'Cl the data expressed as a percentage height reduction EXAMPLE 8 when compared with the untreated check.

Pea Yield Test Solvent: 9.5 m1. of water containing 0.01% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

TABLE 6.-CHEMICAL MOWING OF MERION BLUEGRASS Active Maleic compound hydrazide Percent applied applied Height height Active compound (p.p.m.) (p.p.m.) (cm.) reduction It a 9 Br- CH2N(H'BU)1- Cl 1 Same as above----; 2. 500 0 18. 5 do 1. 250 0 21. 6 1. 667 3. 333 12. 4 34 167 333 19. 0 17 33 17. 5 3. 333 1. 667 14. 0 26 333 167 19. 0 33 17 16. 0 15 0 5. 000 13. 0 31 a in a? (1) .-do..

Control 0 0 18. 8 0

1 Indicates no significant height reduction.

To produce a suitable preparation of the particular active compound 0.5g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rate of application indicated below in p.p.m.

Pea plants, when to of the flowers are in bloom, are sprayed (treated) with the given active compound preparation at a rate of 92.625 decaliters per hec- 26 moist. For each test 40 mls. of the appropriate compound dilution are sprayed on 4 plants in an area of five square feet.

The so-treated plants are moved to a greenhouse and remain there for 2-2 /2 weeks. The sex of the flowers at each node is determined by observation and compared with the check.

The particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 9.

TABLE 9.CUGUMBER SEX EXPRESSION TEST Active compound Plant Node number applied height Active compound (p.p.m.) (cm.) 1 2 3 4 5 6 7 8 9 (1) 800 41.3FFMMFFHFM l 3 9 Br S CH2N(n-Bu)a-Cl Control. 0 45.2 M M M M F M F M M tare. The treatment plots are arranged in a randomized EXAMPLE 10 block design with 3 replications. The control plots receive no such treatment.

At harvest time the fresh weight of fruit from the treated and untreated plots is determined. The increase in yield of the treated plots is expressed as a percentage of the control yield.

The particular active compound tested, the rate of application and the results obtained can be seen from the following Table 8.

TABLE 8.-PEA YIELD TEST Winter Wheat Growth Test Wettable powder base consisting of:

.Active Percent compound increase applied Yield of pea Active compound (p.p.m.) (gJplot) yield Br CHiN(n-Bu);-Cl

(1)-.::':::::*. Same as ahove.. 1 do 10 Control 0 1 EXAMPLE 9 pylene oxide and propylene glycol (mol. wt. about Cucumber Sex Expression Test Wettable powder base consisting of:

92 parts by weight hydrated silica (ultra fine, Hi-Sil 4 parts by weight sodium lignin sulfonate (Marasperse 4 parts by weight polycondensate of ethylene oxide, propylene oxide and propylene glycol (mol. wt. about 1000) (Pluronic L-61) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated Wettable powder base, and the resulting mixture is diluted with water, containing 0.01 polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier, to the desired final concentration.

Cucumber plants (Variety S.N.R. 58), at the two-true leaf stage, i.e., when the plants are about 6-7 days old and are capable of absorbing and translocating chemicals, are sprayed (treated) with the given active compound preparation at the indicated concentration until just dew 1000) (Pluronic L-61l) To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed intimately with 1 part by weight of the stated Wettable powder base, and the resulting mixture is diluted with water, containing 0.01% polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier, to the desired final concentration.

Winter wheat plants, at the 2-3 leaf stage, i.e., when the plants are about 2 weeks old and are capable of absorbing and translocating chemicals, are sprayed (treated) with the given active compound preparation at the indicated concentration until just dew moist. For each test 40 mls. of the appropriate compound dilution are sprayed on 4 plants in an area of five square feet.

The so-treated plants are moved to a greenhouse and remain there for 14-17 days. The degree of growth response is determined by measuring three parameters: total plant height, fresh plant weight and fresh root weight.

Using these parameters, the height reduction of the plant (as compared to the control) and the root/top ratio, are calculated and expressed as percentages.

'Ihe particular active compounds tested, the amounts used and the results obtained can be seen from the following Table 10.

28 EXAMPLE 12 Cotton yield test Solvent: 9.5 ml. of water containing 0.01% by weight of TABLE 10 Percentage P.p.m. of height Fresh Fresh active Plant reduction plant root Root! compound height (compared weight weight top Active compound applied (cm.) to control) (g) (g ratio (1)---. 10, 000 17. 8 36. 4 14. 3 5. 3 58. 3 24. 2 13. 6 15. 8 6. 3 65. 8 B CH 6 B %l 1, 000 21. 8 22. 1 16. 5 7. 73. 7

1' s 2N l1)a' (A) 69 G 10, 000 22. 3 20. 4 18. 5 5. 1 38. 3 ClCHzCHgNMeg-Gl 5, 000 20. 5 26. 8 14. 5 4. 4 46. 7 1, 000 22. 5 19. 6 15. 8 5. 8 57. 5 (known) Control 28. 0 17. O 7. 5 78. 9

EXAMPLE ll polyoxyethylene sorbitan monolaurate (Tween as Chemical pruning of Lombardy poplar trees Solvent: 9.5 ml. of water containing 0.05% by weight of polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

One-year-old Lombardy poplar whips are used as test plants. The trees were pruned back to a uniform height of 91.4 cm. and all lateral branches removed about 1 month before treatment. The entire tree was sprayed in a foliar application with 3 replications, to run-oflf. The retardation of growth is determined by measuring the length of the terminal branch at treatment and again after 6 weeks and after 17 weeks, and thus determining the growth which had occurred after treatment. The growth of this branch is compared with the growth of the terminal branch of untreated trees and expressed as percent inhibition of growth.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in p.p.m.

Cotton plants of the variety Acola 1517C are used as test plants, and are sprayed (treated) with the given active compound preparation at a rate of 185.25 decaliters per hectare, at the initial squaring stage, approximately days after planting. The treatment plots are arranged in a randomized block design with three replications. The control plots receive no such treatment.

The degree of efiicacy of the given active compound is determined by weighing the seed cotton harvested from the given plot. This data is converted to kilograms of cotton yield per hectare, assuming a 35 gin turnout. The percentage increase of cotton lint, when compared with the untreated check, was also determined.

The particular active compound tested, the rates of application and the results obtained can be seen from the 45 following Table 12.

TABLE 12.COTTON YIELD TEXT Active Grams of compound seed applied cotton/ Kg. lint/ Percent Active compound (p.p.m.) it. of row hectare of check GB 9 5 000 27. 7 1 419 108.6 BPL /CHzN(n-Bl1)a'Cl G9 9 (A)- ClCHzGHaNMmCl 10, 000 0. 0 0 0 (known) 5, 000 1. 1 56 4. 3 1, 000 18. O 921 70. 6

Control" The particular compound tested, the rate of application and the results obtained can be seen from the following Table 11.

29 EXAMPLE 13 Soybean yield test Solvent: 9.5 ml. of water containing 0.01% by weight 01 polyoxyethylene sorbitan monolaurate (Tween 20) as emulsifier.

To produce a suitable preparation of the particular active compound, 0.5 g. of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting solution is then further diluted with such solvent containing said emulsifier to provide the rates of application indicated below in gm./ hectare.

Soybean plants of the variety Chippewa 64 are used as test plants, and are sprayed (treated) with the given active compound preparation at a rate of 110 liters per hectare. The treatment was made at a time when the plants were in the 6-8 trifoliate stage with about 50% of the plants having one or more flowers. The treatment plots are arranged in a randomized block design with four replications. The control plots receive no such treatment.

The degree of efiicacy of the given active compound is determined by weighing the beans harvested from the given plot when compared with the untreated check plots.

The particular active compound tested, the rates of application and the results obtained can be seen from the following Table 13.

TABLE 13.-SOYBEAN YIELD TEST 63.5 g. (0.3 M) of 2-bromo-5-thenyl chloride are dissolved in 200 ml. of anhydrous acetonitrile, and 55.5 g. (0.3 M) of tri-n-butyl amine are added. The mixture is heated under reflux for 20 hours.

After removal of the solvent under reduced pressure a pale brown precipitate is formed.

This was recrystallized from 250 ml. of a 4:1 mixture of ethyl acetate/acetonitrile.

101.1 g. (85% of the theory) of 2-bromo-5-theny1 trin-butyl ammonium chloride are obtained, M.P. 157-159 C.

The following compounds are prepared in analogous manner:

Compound number Structure M.P., C.

Gil CH1 B %l 7 11- ll s 5 CH1(nPr) -Cl C! s C] Compound number Structure M.P., 0.

(7) 169-161 I 3 6 Br S CHz'Nfi-CgHlDrCl (8) 153-155 (1 n e e BIxs CHgN(1Bl1):'Cl

CH,N(n-Pr) -O1 Brs -Br 6) Br S CHzNEt -Cl -CHzN(n-Bu);-C1 8 Br- -Br S 63 6 Brs -CHzN(n-Pr)z-0l CH3 J to 6 Br S --CH2N(11-Bu)z-Cl E 60 16 (d) 69 l I 9 Br- S -CHzIiICH2OH.=CHz-C1 Et 32 B CE PI Q' 1P 6 r s r)2-Cl @fi 162 163 C1- CH:N 21

(17) r 2 d 31 e Br- CH2N -Ol lilt e 48 49 9 C1- S -CHgNMe-Cl G3 Br --C HzN-Me- 01 (20) 7 TH: 96-99 G9 9 Bris CHzN-Cl 5.8 g. (0.034 M) of finely powdered silver nitrate are dissolved in boiling anhydrous ethanol (150 ml.). 13.4 g. (0.034 M) of -bromo-2-thenyl-tri-n-butyl ammonium chloride, prepared according to Example 14, was added to the boiling solution.

The white AgCl precipitate, which forms instantly, is allowed to age and then removed by filtration and discarded. The solvent is removed from the filtrate by stripping and the solid residue purified by recrystallization from ethyl acetate.

13.2 g. (94% of the theory) of 5-bromo-2-thenyl-tri-nbutyl ammonium nitrate are obtained, M.P. 114.5 116 C.

The following compounds are prepared in analogous manner:

It will be realized by the artisan that all of the foregoing compounds contemplated by the present invention possess one or more of the desired plant growth regulating properties, as well as a comparatively low phytotoxicity and a concomitantly low mammalian toxicity, enabling such compounds to be used with correspondingly favorable compatibility with warm-blooded creatures for more effective growth-regulating, e.g., growth promoting and growth retarding, purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope 34 of the present invention, which is to be limited only by the scope of the appended claims.

What is claimed is: 1. Quaternary thenyl ammonium salt of the formula (Iii) in which R R and R individually are n-butyl, n-propyl, isopropyl, iso-amyl, iso-butyl or methyl, provided that the total number of carbon atoms in R R and R taken together lies between 9 and 15. X is a chloride, nitrate or thiocyanate ion, and

in Formula Ii R is bromo or chloro, and R is hydrogen, and in Formula Iii R and R are both chloro or both bromo.

2. Salt according to claim 1 in which said salt is (2- bromo-S-thenyl)-(tri-n-butyl)-ammonium chloride of the formula 1 Br-LS LOH N(n-Bu);.Cl

3. Salt according to claim 1 in which said salt is (2- bromo-S-thenyl)-(tri-n-butyl)-ammonium nitrate of the formula 4. Salt according to claim 1 in which said salt is (2- bromo-5-thenyl)-(tri-n-butyl)-ammonium thiocyanate of the formula 5. Salt according to claim 1 in which said salt is (2- chloro-S-thenyl)-(tri-n-butyl)-ammonium chloride of the formula 6. Salt according to claim 1 in which said salt is (2,5- dichloro-4-thenyl)-(tri-n-propyl)-ammonium chloride of the formula 8. Salt according to claim 1 in which said salt is (2- bromo-S-thenyl)-(tris-iso-amyl)-ammonium chloride of the formula y Br slCHgNfl-Cflinh-Cl (References on following page) 35 References Cited Goldfarb, et a1., Chem. Abs. 55 :13862-3 (10/1956).

2,548,898 4/ 1951 Kyrides 260-429 HENRY R. IILES, Primary Examiner OTHER REFERENCES 5 C. M. S. IAISLE, Assistant Examiner Hartough, et aL, Chem. Abs. 43:1763-4 (3/ 1949). CL

Hartough, et a1. II, Chem. Abs. 45: 151-2 (3/1951). Weilmuenster, et a1., Chem. Abs. 47:1686-7 3/1953). 261F247", 326-84, 329 AM, 332-2 C; 71-90 Smith, et a1., Chem. Abs. 49:6221-2 (5/1955). 10

"W050 UNITED STATES PATENT OFFICE V '1 1 I CERTIFICATE OF CORRECTION I Patent No- 3,748,343 Dated July 24, 1973 I -G) Peter F. Epstein et al. I I

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 4, 1ine 45 Compound (1) change "ethenyl" to ---thenyl--.

Col, 5, line 66 Compound (-55), change "dis" to --di--. Col. 8, line 24, change "moving" to --mowing.

7 Col. 9, line 6l,change "wall" to --well,-.

Col. 10, line 44, change "bol" to --mol--; a Col. 13, Compound (36) change formula from 'nhLg g fi Col. 13, Compound (37) ,under heading "Concentration(p.p.m.)

insert --4-- under column "100" Col. 15, Table 2, Compound (4). change to Col. 15, Table 2, Compound (6) change formula from H (AL J o Col. 21, line 51, before "mixed" insert is Col. 23, line 1, change "Marion" to Marion Col. 23, Table 6 in the title, change "Marion" to --Marion--.

L Col. 23, Table 6; delete decimal points in first two columns w UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3,748,343 Dated July 24, 1973 Inventofls) Peter F. Epstein et a1 Page 2 I It is certified that error appears" in the aboye-identified patent and that said Letters Patent are hereby corrected as shown below:

. 3 "1 Col. 29,, line 45, 1 Example 14 Compound (1) change "C1" to 6 c1 Col. 29, Compound (5) in the formula, insert --N after "CH2".

Col. 30, Compound (8) in the formula, under "N" insert 6 Col. 31, Compound (35) in the formula, between "CH" and "CH change single bond to double bond Col. 31, Compound (37) in the formula, change"1" to C1--. C01. 31, Compound (38) in the formula, change "E1" to 81 C01. 33, Compound (54) under heading "M.P. C"jchange "154.2"

to 154.5. u 7 C Col. 33, Compound (52) in the formula, above" H insert Col. 33, Compound 6) insert -5-- before "6" (Compound (56),)

Same Compound (56) over "N" insert -9 Signed and sealed this 9th day of July 1974 (SEAL) Attest: I

MCCOY M. GIBSON, JR. (3. MARSHALL DANN Attesting offi 1 7 Commissioner of Pa-tehts 

